JPH0733579A - Production of fine single crystal powder - Google Patents

Abstract

PURPOSE:To provide a method for producing fine single crystal powder in which the fine single crystal of a perovskite structure having a uniform composition and grain diameter and a high crystallinity is synthesized at a lower temperature. CONSTITUTION:This method for producing fine single crystal powder is to mix respective oxides of X, M and G or compounds of the X, M and G convertible into the oxides thereof so as to provide <0.1mum diameter thereof, bake the resultant mixture, afford a dielectric composition expressed by the general formula wXMO3-(1-w)(XOy-aGOz) [X is one or two or more selected from Li, Na, K, Pb, Ba, Mg, Ca, Sr, La, Y and Bi; M is one or two or more selected from Al, Mn, Ti, Zr, Sn, Mg, Zn, Fe, Co, Ni, Nb, Ta and W; G is one or two or more selected from B, As, Sb, Si, Ge, Te and P; (y) and (z) denote the number of oxygen; (w) denotes the number of mol; (a) is a real number; 0.1<(w)<=0.95; 0.05<=(a)<=21, then dissolve and remove glassy components therefrom with an acid or an alkali and provide this fine single crystal powder.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a fine single crystal powder, and more particularly to a method for producing a fine single crystal powder having a perovskite structure in which each particle is a single crystal having a uniform grain size. is there. The fine single crystal powder obtained by the present invention can be applied as a piezoelectric composite to piezoelectric components such as actuators and pressure-sensitive sensors, and to phosphor materials by doping with rare earth ions.

[0002]

2. Description of the Related Art Conventionally, dielectric powders such as barium titanate and lead zirconate titanate have been used as materials for porcelain capacitors and filters due to their dielectric and piezoelectric characteristics. These powders are generally manufactured as a dielectric powder of 0.5 to 5 μm by a solid phase reaction by firing powders of oxides, carbonates and the like at a high temperature or a coprecipitation method by a solution reaction in an aqueous solution.

In any of these reactions, the powder obtained is composed of secondary particles formed by agglomeration of primary particles, and there is a problem in composition uniformity and crystallinity. A hydrothermal synthesis method has been proposed to solve this problem, but the method requires high temperature and high pressure, and the cost is high due to equipment cost, productivity, and the like. Therefore, as another method, a method using crystallized glass has been proposed.

In this method, the compound is first mixed in a composition capable of forming glass, melted at a high temperature of about 1400 ° C., and then rapidly cooled to form glass, which is then heated to 600-
A fine single crystal is obtained by crystallization by heat treatment at 800 ° C. In this method, the composition that can be vitrified is extremely limited, and it was extremely difficult to increase the proportion of the crystal phase to more than 50%.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a manufacturing method capable of synthesizing a fine single crystal powder having a perovskite structure having a uniform composition, a high crystallinity, and a uniform grain size at a lower temperature. It is a thing.

[0006]

In view of such circumstances, the inventors of the present invention have made earnest studies on a fine single crystal powder having a perovskite structure, and as a result, have found a manufacturing method thereof and completed the present invention.

That is, the present invention is as follows. 1) X oxide (X is Li, Na, K, Pb, Ba, M
One or more selected from g, Ca, Sr, La, Y and Bi) and an oxide of M (M is Al, Mn, Ti, Z).
r, Sn, Mg, Zn, Fe, Co, Ni, Nb, T
a, one or more selected from W), an oxide of G (G is one or more selected from B, As, Sb, Si, Ge, Te, P) or an oxidation thereof. X compounds, M compounds, and G compounds that can be converted into compounds are mixed so that the diameter of each oxide or compound is less than 0.1 μm, and the mixture is calcined to give the general formula wXMO _3- (1-w).
(XO _y -aGO _z) (wherein, y, z represents the number of oxygen atoms,
When X is Li, Na, K, y = 0.5, X is Pb, B
When a, Mg, Ca, and Sr, y = 1, X is La, Y,
In the case of Bi, y = 1.5. When G is B, As, Sb, z = 1.5, when G is Si, Ge, Te, z =
When 2, G is P, z = 2.5. w represents the number of moles, a is a real number, and 0.1 <w ≦ 0.95, 0.05 ≦ a
≦ 2. ) Is obtained, and the glass component is dissolved and removed therefrom with an acid or an alkali, and a method for producing a fine single crystal powder.

2) X compound soluble in an organic solvent (X is L
i, Na, K, Pb, Ba, Mg, Ca, Sr, La,
One or more selected from Y and Bi), M compound (M is Al, Mn, Ti, Zr, Sn, Mg, Zn, F)
e, Co, Ni, Nb, Ta, W, one or more selected from, and G compounds (G is B, As, Sb, Si,
Ge, Te, or P) selected from the above, each solution is mixed, dried or hydrolyzed to form a mixed powder having a diameter of each compound of less than 0.1 μm, and then calcined. General formula wXMO _3- (1-w) (X
O _y -aGO _z) (wherein, y, z represents the number of oxygen atoms, X is Li, Na, y = 0.5 When the K, X is Pb, Ba,
When Mg, Ca, Sr, y = 1, X is La, Y, Bi
Then y = 1.5. When G is B, As, Sb, z = 1.5, when G is Si, Ge, Te, z = 2,
When G is P, z = 2.5. w represents the number of moles,
a is a real number, 0.1 <w ≦ 0.95, 0.05 ≦ a ≦ 2
Is. ) Is obtained, and the glass component is dissolved and removed therefrom with an acid or an alkali, and a method for producing a fine single crystal powder.

3) X having a primary particle size of less than 0.1 μm
Compound (X is Li, Na, K, Pb, Ba, Mg, C
a, Sr, La, Y, one or more selected from Bi), M compound (M is Al, Mn, Ti, Zr, S)
n, Mg, Zn, Fe, Co, Ni, Nb, Ta, W, or a combination thereof, a G compound (G is B,
One or more colloidal sols selected from As, Sb, Si, Ge, Te, and P) are used, and each colloidal sol is mixed and dried or coprecipitated so that each compound has a diameter of 0. A mixed powder having a size of less than 1 μm is formed and then fired to obtain a powder having the general formula wXMO _3- (1-w) (XO _y -a
GO _z ) (In the formula, y and z represent oxygen numbers, and X represents Li and N.
a = K, y = 0.5, X = Pb, Ba, Mg, C
When a and Sr, y = 1, and when X is La, Y, and Bi, y = 1.5. When G is B, As, Sb, z =
1.5, when G is Si, Ge, Te, z = 2, G is P
Then z = 2.5. w represents the number of moles, a is a real number, and 0.1 <w ≦ 0.95 and 0.05 ≦ a ≦ 2. ) Is obtained, and the glass component is dissolved and removed therefrom with an acid or an alkali, and a method for producing a fine single crystal powder.

4) Water-soluble X compound (X is Li, N
a, K, Pb, Ba, Mg, Ca, Sr, La, Y, B
1 or more selected from i), M compound (M is Al, Mn, Ti, Zr, Sn, Mg, Zn, Fe, C)
one or more selected from o, Ni, Nb, Ta and W), G compound (G is B, As, Sb, Si, Ge,
(One or more selected from Te and P) are used, and the respective solutions are mixed, dried or co-precipitated to obtain a mixed powder having a diameter of each compound of less than 0.1 μm, and then fired to form a powder. Formula wXMO ₃ − (1-w) (XO _y −a
GO _z ) (In the formula, y and z represent oxygen numbers, and X represents Li and N.
a = K, y = 0.5, X = Pb, Ba, Mg, C
When a and Sr, y = 1, and when X is La, Y, and Bi, y = 1.5. When G is B, As, Sb, z =
1.5, when G is Si, Ge, Te, z = 2, G is P
Then z = 2.5. w represents the number of moles, a is a real number, and 0.1 <w ≦ 0.95 and 0.05 ≦ a ≦ 2. ) Is obtained, and the glass component is dissolved and removed therefrom with an acid or an alkali, and a method for producing a fine single crystal powder.

5) Hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid as acids
The method for producing a fine single crystal powder as described in the above item 1, 2, 3 or 4, characterized in that an aqueous solution of one or more selected from acetic acid is used.

6) The above 1, 2, 3 characterized in that an aqueous solution of one or more selected from sodium hydroxide, potassium hydroxide and ammonia is used as the alkali.
Alternatively, the method for producing a fine single-crystal powder according to item 4.

The present invention will be described in more detail below. The present invention relates to an oxide of X [X is Pb, Ba, Li, Na, K,
1 or 2 selected from Mg, Ca, Sr, La and Y
Or more (hereinafter referred to as X)], an oxide of M [M is T
i, Zr, Sn, Mg, Zn, Fe, Co, Ni, Nb
One or more selected from the following (hereinafter referred to as M)], an oxide of G [G is B, As, Sb, Si, G
One or more selected from e, Te and P (hereinafter,
Referred to as G)] or X compounds can be converted to these oxides, M compound, using a G compound, general formula WXMO ₃
-(1-w) (XO _y -aGO _z ), a method for producing a fine single crystal powder by dissolving and removing a glass component from the dielectric composition with an acid or an alkali. It is about.

Here, y and z represent oxygen numbers, and X represents L.
When i, Na, K, y = 0.5, X is Pb, Ba, M
When g, Ca, Sr, y = 1, and when X is La, Y, Bi, y = 1.5. When G is B, As, Sb, z = 1.5, when G is Si, Ge, Te, z = 2, G
When is P, z = 2.5. w represents the number of moles, a
Is a real number, and 0.1 <w ≦ 0.95 and 0.05 ≦ a ≦ 2.

W is the ratio of the dielectric crystal phase, which is 0.1
In the following cases, too little fine single crystal powder is obtained,
If it exceeds 0.95, it is difficult to produce a fine single crystal powder, and high temperature is required. Further, w may be in the above range in order to desirably control the particle size of the fine single crystal powder, the generation temperature, and the like. y is 1 / of the total valence obtained by multiplying the valence of each ion composing X by the mole fraction from the request of electrical neutrality.
It is 2. a represents the number of moles of the glass phase forming oxide based on the element. For example, in the case of boric acid (B ₂ O ₃ ), BO
_1.5 is 1 mol, in the case of P ₂ O ₅ , PO _2.5 is 1 mol,
In the case of the SiO ₂ to the SiO ₂ and 1 mol. Also, 1
/ A represents the molar ratio of the element X present in the glass phase to G, and the molar ratio is preferably 0.5 to 20 times, more preferably 1 to 9 times. When 1 / a is smaller than 0.5, X escapes from the compound in the crystal phase to reduce the amount of crystal phase, and when it is more than 20, excess XO is precipitated and the crystal phase is also reduced. To do.

In the practice of the present invention, as a method of obtaining a mixed powder in which each oxide of X, M, G as a starting material or a compound thereof has a diameter of less than 0.1 μm, a CVD method or an organic solvent is used. There are a method using a soluble compound, a method using a colloidal sol such as silica colloid, and a method using a water-soluble compound.

In the case of the CVD method, the X compounds as starting materials include the following. -Lithium compounds such as lithium hydride and alkyl lithium. -Sodium compounds such as sodium hydride and alkyl sodium. -Potassium compounds such as potassium hydride and alkyl potassium. -Organic lead compounds such as 4-ethyl lead and bis-dipivaloylmethanato lead, or lead compounds such as lead chloride such as lead chloride. -Organic barium compounds such as barium ethoxide, barium isopropoxide and bisdipivaloyl barium, or halide barium compounds such as barium chloride. -Organomagnesium compounds such as magnesium ethoxide, magnesium isopropoxide, and bisdipivaloyl magnesium, or halide magnesium compounds such as magnesium chloride. -Organic calcium compounds such as calcium ethoxide, calcium isopropoxide and bisdipivaloyl calcium, or halide calcium compounds such as calcium chloride. -Organic strontium compounds such as strontium ethoxide, strontium isopropoxide and bisdipivaloyl strontium, or halide strontium compounds such as strontium chloride. -Organic lanthanum compounds such as lanthanum ethoxide, lanthanum acetylacetonate and bisdipivaloyl lanthanum, or halide lanthanum compounds such as lanthanum chloride. -Organic yttrium compounds such as yttrium ethoxide, yttrium acetylacetonate and bis-dipivaloyl yttrium, or halide yttrium compounds such as yttrium chloride. -Organic bismuth compounds such as bismuth ethoxide, bismuth acetylacetonate and bisdipivaloylbismuth, or bismuth compounds of halides such as bismuth chloride.

In the case of the CVD method, the M compound as a starting material includes the following.・ Trimethyl aluminum, triethyl aluminum,
Aluminum compounds such as aluminum triisopropoxide, or halogenated aluminum compounds such as aluminum chloride. -Manganese compounds such as manganese acetylacetonate. -Organic titanium compounds such as titanium ethoxide, titanium isopropoxide, titanium butoxide, and titanium acetate, or halide titanium compounds such as titanium tetrachloride. Organic zirconium compounds such as zirconium ethoxide, zirconium isopropoxide, zirconium butoxide, or zirconium compounds of halides such as zirconium tetrachloride. Organic such as tetraethyltin, tetrabutyltin, tin ethoxide, tin isopropoxide, tin butoxide. Tin compounds. -Organomagnesium compounds such as magnesium ethoxide, magnesium isopropoxide, and bisdipivaloyl magnesium, or halide magnesium compounds such as magnesium chloride. -Organic zinc compounds such as zinc ethoxide, zinc acetylacetonate and bisdipivaloyl zinc, or halide zinc compounds such as zinc chloride. -Organic iron compounds such as iron ethoxide, iron acetylacetonate, and bisdipivaloyl iron, or halide iron compounds such as iron chloride. -Organic cobalt compounds such as cobalt ethoxide, cobalt acetylacetonate, and bisdipivaloyl cobalt, or halide cobalt compounds such as cobalt chloride. -Organic nickel compounds such as nickel ethoxide, nickel acetylacetonate and bisdipivaloyl nickel, or halide nickel compounds such as nickel chloride. -Organic niobium compounds such as niobium ethoxide, niobium acetylacetonate and bisdipivaloyl niobium, or halide niobium compounds such as niobium chloride. -Organic tantalum compounds such as tantalum ethoxide, tantalum acetylacetonate, and bisdipivaloyl tantalum, or halide tantalum compounds such as tantalum chloride. -Organic tungsten compounds such as tungsten ethoxide, tungsten acetylacetonate, and bisdipivaloyl tungsten, or halide tungsten compounds such as tungsten chloride.

In the case of the CVD method, the G compound as a starting material includes the following. Boron, triethylboron, trimethylboron and other boron compounds. -Arsenic compounds such as arsine, triethylarsenic, trimethylarsenic and the like. • Antimony compounds such as triethyl antimony and trimethyl antimony. -Silicon compounds such as silane, disilane, tetramethylsilane, tetraethylsilane, silicon tetrachloride, tetraethoxysilane, and tetramethoxysilane. -Germanium compounds such as germanium hydride, tetramethyl germanium, tetraethyl germanium, germanium tetrachloride, tetraethoxy germanium and tetramethoxy germanium. Tellurium compounds such as hydrogenated tellurium, tetramethyl tellurium, tetraethyl tellurium, tellurium tetrachloride, tetraethoxy tellurium, and tetramethoxy tellurium. -Phosphorus compounds such as phosphorus oxychloride.

Each of these compounds has a diameter of 0.1.
mixed so as to be less than μm, and the general formula wXMO ₃ − (1
-W) (XO _y composition represented by -aGO _z) is precipitate in the reactor so as to obtain. Here, as the mixing method, as is commonly used, the method of mixing each compound vaporized by an individual vaporizer in the middle of the pipe has good controllability, but all the raw materials are mixed in advance as compounds having almost the same vapor pressure. You may vaporize afterwards.

The gas flow rate is 100c depending on the production rate.
It can be selected in the range of c / min to 10 liters / min.

Any reactor can be used as long as it has a corrosion resistance and can mix the gas under the condition of being shielded from the outside air.

The reactor wall or substrate is 300 to 900 ° C.
However, fine single crystals are directly deposited when heated. Since amorphous powder is generally used when it is not heated, the powder is taken out from the CVD apparatus and then heated to deposit a fine single crystal.

As a method for firing the mixed powder having the diameter of each compound of X, M, and G thus obtained and having a diameter of less than 0.1 μm, known methods such as electric resistance heating, plasma, high frequency, and laser can be used. it can. The firing temperature varies depending on the manufacturing method, but in the case of the CVD method, it may be in the range of 200 to 900 ° C.

The firing may be carried out in air, an inert gas or a reducing atmosphere. When the fine single crystal powder is easily reduced, it can be fired in an oxygen atmosphere.

The powder thus obtained is a mixture of a large number of precipitated fine single crystals and glass components. In order to separate only the fine single crystal from this, a means of filtering and centrifuging can be used after dissolving the glass component in an aqueous solution of water, dilute acid, dilute alkali or the like.

Examples of the acid used here include nitric acid, hydrofluoric acid, hydrochloric acid, sulfuric acid, acetic acid and the like, and they can be used alone or in a mixture. Examples of the alkali include ammonia water, caustic soda, caustic potash, and the like, and they can be used alone or in combination. These are used after diluting to a concentration of 5 to 50% by weight.

In the method using a compound soluble in an organic solvent, the X compound includes the following. -Lithium compounds such as ethoxylithium, isopropoxylithium, butoxylithium, lithium acetate and lithium acetylacetonate. -Sodium compounds such as sodium methoxy, diethoxy sodium, sodium diisopropoxy, sodium dibutoxy, sodium acetate and sodium acetylacetonate. -Potassium compounds such as methoxy potassium, ethoxy potassium, diisopropoxy potassium, butoxy potassium, potassium acetate, potassium acetylacetonate and the like. -Lead compounds such as diethoxylead, diisopropoxylead, dimethoxyethoxylead, lead acetylacenate, lead formate and lead acetate. -Barium compounds such as dimethoxybarium, diethoxybarium, diisopropoxybarium, dibutoxybarium, barium acetate and barium acetylacetonate.・ Dimethoxy magnesium, diethoxy magnesium,
Magnesium compounds such as diisopropoxy magnesium and dibutoxy magnesium. -Calcium compounds such as dimethoxy calcium, diethoxy calcium, diisopropoxy calcium and dibutoxy calcium. -Strontium compounds such as dimethoxystrontium, diethoxystrontium, diisopropoxystrontium and dibutoxystrontium. Lanthanum compounds such as trimethoxylanthanum, triethoxylanthanum, triisopropoxylanthanum, tributoxylanthanum and lanthanum chloride. -Yttrium compounds such as trimethoxy yttrium, triethoxy yttrium, triisopropoxy yttrium, tributoxy yttrium and yttrium chloride. Bismuth compounds such as trimethoxybismuth, triethoxybismuth, triisopropoxybismuth, tributoxybismuth, bismuth chloride.

In the method using a compound soluble in an organic solvent, the M compound includes the following.・ Trimethyl aluminum, triethyl aluminum,
Aluminum compounds such as aluminum triisopropoxide, or halide aluminum compounds such as aluminum chloride. -Manganese compounds such as manganese acetylacetonate. -Titanium compounds such as tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium and titanium tetrachloride. -Zirconium compounds such as tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxyzirconium, tetrabutoxyzirconium and zirconium tetrachloride. -Tin compounds such as tetramethoxytin, tetraethoxytin, tetraisopropoxytin, tetrabutoxytin, tetraoctyltin, tin acetylacetonate and tin tetrachloride.・ Dimethoxy magnesium, diethoxy magnesium,
Magnesium compounds such as diisopropoxy magnesium and dibutoxy magnesium. -Zinc compounds such as dimethoxyzinc, diethoxyzinc, diisopropoxyzinc, dibutoxyzinc, zinc acetylacetonate and zinc chloride. -Iron compounds such as tetraethoxy iron, tetraisopropoxy iron, tetrabutoxy iron, iron acetylacetonate, and iron chloride. -Cobalt compounds such as tetraethoxy cobalt, tetraisopropoxy cobalt, tetrabutoxy cobalt, cobalt acetylacetonate, and cobalt chloride. -Nickel compounds such as tetraethoxy nickel, tetraisopropoxy nickel, tetrabutoxy nickel, nickel acetylacetonate, and nickel chloride. -Niobium compounds such as pentamethoxy niobium, pentaethoxy niobium, pentaisopropoxy niobium, pentabtox niobium, niobium chloride.・ Pentamethoxytantalum, pentaethoxytantalum,
Tantalum compounds such as pentaisopropoxy tantalum, pentab toxtantalum and tantalum chloride. -Tungsten compounds such as pentamethoxytungsten, pentaethoxytungsten, pentaisopropoxytungsten, pentabtoxytungsten, and tungsten chloride.

In the method using a compound soluble in an organic solvent, the G compound includes the following. Boron compounds such as triethyl borate, trimethyl borate, trimethoxyethoxy boron, triphenyl borate and boric acid. Arsenic compounds such as triethyl arsenate, trimethyl arsenate, trimethoxyethoxy arsenic, triphenyl arsenate, etc.・ Triethyl antimonate, trimethyl antimonate,
Antimony compounds such as trimethoxyethoxy antimony and triphenyl antimonate. -A silicon compound such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane and silicon tetrachloride. -Germanium compounds such as tetramethoxy germanium, tetraethoxy germanium, tetraisopropoxy germanium, tetrabutoxy germanium and germanium tetrachloride. A tellurium compound such as tetramethoxy tellurium, tetraethoxy tellurium, tetraisopropoxy tellurium, tetrabutoxy tellurium, or tellurium tetrachloride. -Phosphorus compounds such as trimethoxyphosphonium and phosphorus oxychloride.

As the organic solvent used in carrying out the present invention, the lithium compound, sodium compound, potassium compound, lead compound, barium compound, magnesium compound, calcium compound, strontium compound,
Lanthanum compounds, yttrium compounds, bismuth compounds, aluminum compounds, manganese compounds, titanium compounds, zirconium compounds, tin compounds, zinc compounds, iron compounds, cobalt compounds, nickel compounds, niobium compounds, tantalum compounds, tungsten compounds,
Any organic solvent may be used as long as it dissolves a boron compound, an arsenic compound, an antimony compound, a silicon compound, a germanium compound, a tellurium compound, a phosphorus compound, etc., but preferably methanol, ethanol, propanol, butanol, Alcohols such as pentanol, methoxyethanol, ethoxyethanol, benzene,
Aromatic hydrocarbons such as toluene and xylene, pentane,
Hexane, heptane, octane and other aliphatic hydrocarbons,
Ethers such as dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and diethyl ketone, carboxylic acid esters such as methyl acetate, ethyl acetate and ethyl formate, β-diketones such as acetylacetone, benzoylacetone and dibenzoylacetone, dimethyl Examples thereof include amides such as formamide and dimethylacetamide. These organic solvents can be used alone or in combination of two or more kinds.

The general formula wXMO _3- (1-w) (XO _y-
aGO _z ), the compound solution for preparing the composition may be prepared by dissolving the X compound, the M compound and the G compound in an organic solvent and mixing them at room temperature. A method of reacting in a solvent under heating can be mentioned.

The temperature for heating in the organic solvent varies depending on the kind of the compound, but is in the temperature range of 60 to 150 ° C., and the method of heating the reaction vessel with a jacket is standard.

In the method using a compound soluble in an organic solvent, the concentration of each compound in the solution for forming a fine single crystal powder varies depending on the kind of compound, but if it is diluted too much, a large amount of solvent is required. It is not economical and is generally 5 to 80% by weight in terms of oxide, preferably 10 to
Applied at 50% by weight.

The solution for forming the fine single crystal powder used here includes a stabilizing carboxylic acid (C6 to C20),
Glycols, amines and the like can be added. Also,
In order to improve the workability of the solution for forming a fine single crystal powder,
For example, high molecular substances such as polyol and ethyl cellulose,
A high boiling point compound such as methyl cellosolve, ethyl cellosolve, acetylacetone and glycerin, a nonionic or anionic surfactant, and the like can be added.

The solution thus obtained is dried or hydrolyzed so that each compound of X, M and G has a diameter of 0.1 μm.
A mixed powder of less than m can be obtained. The hydrolysis is carried out by reacting with water or a solution containing water in excess of at least twice the number of moles of the compound contained in the solution of the compound, or by simply leaving it in the air to react with water in the air. You may let me.

As a method for drying the powder obtained here, a known method such as a rotary evaporator, a flaker and an air bath can be used.

As a firing method, known methods such as electric resistance heating, plasma, high frequency, laser and the like can be used. Here, the firing temperature varies depending on the kind of the compound, but it needs to be higher than the crystallization of the fine single crystal powder, and is usually 400 to 1200 ° C., preferably 500 to 1.
It is 000 ° C. Organic matter does not decompose below 400 ° C,
Crystallization does not proceed either. Further, if the temperature exceeds 1200 ° C., the composition is changed due to element evaporation and the like, which is not preferable.

The calcination may be performed in air, an inert gas or a reducing atmosphere. When the fine single crystal powder is easily reduced, it can be fired in an oxygen atmosphere.

The powder thus obtained is a mixture of a large number of precipitated fine single crystals and a glass component. In order to separate only the fine single crystal from this, a means of filtering and centrifuging can be used after dissolving the glass component in an aqueous solution of water, dilute acid, dilute alkali or the like.

Examples of the acid used here include nitric acid, hydrofluoric acid, hydrochloric acid, sulfuric acid, acetic acid and the like, and they can be used alone or in a mixture. Examples of the alkali include ammonia water, caustic soda, caustic potash, and the like, and they can be used alone or in combination. These are used after diluting to a concentration of 5 to 50% by weight.

The general formula wXMO _3- (1-w) (XO _y-
aGO _z ), a method using a colloidal sol to obtain a composition represented by X compound, M compound, G
The colloidal sol of each compound is prepared, for example, by precipitation of a water-soluble salt such as chloride, nitrate, sulfate, or acetate of each compound with an alkali, or ion exchange. Further, as silica, a commercially available silica sol (manufactured by DuPont, Nissan Chemical Co., Ltd., Catalyst Chemical Industries, etc.) can be used.

These colloidal sols have the general formula wXMO ₃
- (1-w) (XO y -aGO z) were mixed so as to satisfy, drying or coprecipitated, gelled, etc. and gel powder, resulting X, M, the diameter of each compound G 0 Gel powders of less than 1 μm are crushed if necessary.

Drying is usually mentioned as a gelation method. Generally, the sol loses its repulsive force when the dispersion medium is exhausted, and gels. This method can be applied to all sols. In addition, even if the Coulomb repulsion is suppressed by adjusting the pH or adding salt, gelation occurs. The acidic sol gels in the neutral to alkaline region by adding ammonia or caustic soda, and the alkaline sol gels in the neutral to acidic region by adding an acid such as hydrochloric acid or nitric acid. Potassium chloride,
When a salt such as calcium chloride or aluminum nitrate is added to increase the electrolyte concentration of the aqueous colloid solution, the Coulomb repulsion force is shielded and becomes smaller, resulting in gelation. Gelation can also occur by adding an organic solvent such as isopropanol or acetone.

As a method for drying the powder obtained here, a known method such as a rotary evaporator, a flaker and an air bath can be used.

As the firing method, known methods such as electric resistance heating, plasma, high frequency, laser, etc. can be used. Here, the firing temperature varies depending on the kind of the compound, but it needs to be higher than the crystallization of the fine single crystal powder, and is usually 400 to 1200 ° C., preferably 500 to 1.
It is 000 ° C. Organic matter does not decompose below 400 ° C,
Crystallization does not proceed either. Further, if the temperature exceeds 1200 ° C., the composition is changed due to element evaporation and the like, which is not preferable.

The calcination may be carried out in air, an inert gas or a reducing atmosphere. When the fine single crystal powder is easily reduced, it can be fired in an oxygen atmosphere.

The powder thus obtained is a mixture of a large number of precipitated fine single crystals and a glass component. In order to separate only the fine single crystal from this, a means of filtering and centrifuging can be used after dissolving the glass component with water or an aqueous solution of dilute acid, dilute alkali or the like.

Examples of the acid used here include nitric acid, hydrofluoric acid, hydrochloric acid, sulfuric acid, acetic acid and the like, and they can be used alone or in a mixture. Examples of the alkali include ammonia water, caustic soda, caustic potash, and the like, and they can be used alone or in combination. These are used after diluting to a concentration of 5 to 50% by weight.

In the method of mixing a water-soluble compound and optionally coprecipitating to obtain a mixture, the X compound includes the following. -Lithium compounds such as lithium nitrate, lithium acetate and lithium chloride. -Sodium compounds such as sodium nitrate, sodium acetate and sodium chloride. -Potassium compounds such as potassium nitrate, potassium acetate and potassium chloride. -Lead compounds such as lead nitrate, lead acetate and lead chloride. -Barium compounds such as barium nitrate, barium acetate and barium chloride. -Magnesium compounds such as magnesium nitrate, magnesium acetate, and magnesium chloride. -Calcium compounds such as calcium nitrate, calcium acetate and calcium chloride. -Strontium compounds such as strontium nitrate, strontium acetate, and strontium chloride. Lanthanum compounds such as lanthanum nitrate, lanthanum acetate, lanthanum chloride. -Yttrium compounds such as yttrium nitrate, yttrium acetate, and yttrium chloride. Bismuth compounds such as bismuth nitrate, bismuth acetate and bismuth chloride.

Examples of the water-soluble M compound include the following. -Aluminum compounds such as aluminum nitrate, aluminum acetate, aluminum chloride and aluminum sulfate. -Manganese compounds such as manganese nitrate, manganese acetate, and manganese chloride. -Titanium compounds such as titanyl nitrate, titanyl acetate, titanium tetrachloride, and titanyl sulfate. -Zirconium compounds such as zirconyl nitrate, zirconyl acetate, zirconium tetrachloride and zirconyl sulfate. -Tin compounds such as tin nitrate, tin acetate, tin tetrachloride and tin dichloride. -Magnesium compounds such as magnesium nitrate, magnesium acetate, and magnesium chloride. -Zinc compounds such as zinc nitrate, zinc acetate, zinc chloride and zinc sulfate. -Iron compounds such as iron nitrate, iron chloride, and iron sulfate. -Cobalt compounds such as cobalt nitrate, cobalt acetate, cobalt chloride, and cobalt sulfate. -Nickel compounds such as nickel nitrate, nickel acetate, nickel chloride, and nickel sulfate. -Niobium compounds such as niobium nitrate, niobium acetate, niobium chloride and niobium sulfate. -Tantalum compounds such as tantalum nitrate, tantalum acetate, tantalum chloride, and tantalum sulfate. -Tungsten compounds such as tungsten nitrate, tungsten acetate, tungsten chloride, and tungsten sulfate.

Examples of water-soluble G compounds include the following. -Boron compounds such as boric acid. -Arsenic compounds such as arsenic acid. -Antimony compounds such as antimonic acid, antimony nitrate, antimony acetate, thymon chloride, and antimony sulfate. -Silicon compounds such as silicon tetrachloride and silicic acid. -Germanium compounds such as germanium tetrachloride, germanium nitrate, and germanium acetate. • Tellurium compounds such as tellurium tetrachloride and tellurium nitrate. -A phosphorus compound such as phosphoric acid.

The above water-soluble compound is represented by the general formula wXMO ₃
- (1-w) (XO y -aGO z) were mixed so as to satisfy, to adjust the pH, to obtain a precipitate by adding an anion such as to produce a sparingly soluble salt, and drying the X, A mixed powder in which each compound of M and G has a diameter of less than 0.1 μm is obtained, and pulverized as necessary.

The pH for forming a precipitate varies depending on the compound, but generally, the pH is preferably 3 or more and around neutral. The pH is 1 for alkaline earth metal ions such as Mg.
One or more is required, and in the case of alkali metal ions, precipitation does not occur by adjusting the pH. Therefore, in the case of alkaline earth metal ions, the formation of a sparingly soluble salt is preferable, and the addition of oxalic acid, sulfuric acid, citric acid or the like causes precipitation. In the case of an alkali metal ion, precipitation is caused due to a decrease in solubility by removing water from the system.

As a method for drying the powder obtained here, a known method such as a rotary evaporator, a flaker and an air bath can be used.

As the firing method, known methods such as electric resistance heating, plasma, high frequency, laser and the like can be used. Here, the firing temperature varies depending on the kind of the metal compound, but it is necessary to set it to a temperature equal to or higher than the crystallization of the fine single crystal powder, and usually 400 to 1200 ° C, preferably 500 to
It is 1000 ° C. If the temperature is lower than 400 ° C., organic substances are not decomposed and crystallization does not proceed. Further, if the temperature exceeds 1200 ° C., the composition is changed due to element evaporation and the like, which is not preferable.

The firing may be performed in air, an inert gas or a reducing atmosphere. When the fine single crystal powder is easily reduced, it can be fired in an oxygen atmosphere.

The powder thus obtained is a mixture of a large number of precipitated fine single crystals and glass components. In order to separate only the fine single crystal from this, a means of filtering and centrifuging can be used after dissolving the glass component with water or an aqueous solution of dilute acid, dilute alkali or the like.

Examples of the acid used here include nitric acid, hydrofluoric acid, hydrochloric acid, sulfuric acid, acetic acid and the like, and they can be used alone or in a mixture. Examples of the alkali include ammonia water, caustic soda, caustic potash, and the like, and they can be used alone or in combination. These are used after diluting to a concentration of 5 to 50% by weight.

[0060]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The crystal phase was confirmed by powder X-ray diffraction, and the crystal shape was confirmed by a scanning electron microscope.

Example 1 Lead diethoxide, titanium tetraisopropoxide and trimethyl boron were added to wPbTiO _3- (1-w).
(PbO-BO _1.5 ) and mixed in a ratio as shown in Table 1, dissolved in a 1: 1 (weight ratio) mixed solvent of isopropanol-toluene, and 15% by weight in terms of oxide of a fine single crystal. A powder forming liquid was synthesized. The solvent was removed from this solution by a rotary evaporator, and then the solution was dried at 130 ° C. for 30 minutes to obtain a gel powder. This powder was kept at 800 ° C. for 1 hour to precipitate a fine single crystal powder. 4 more
After washing in 1N nitric acid at 0 ° C., filtration was performed to obtain only fine single crystals. Formation of a crystalline phase was confirmed by X-ray diffraction. The crystal phase peak height (110) was used as a measure of the crystal phase production amount and crystallinity.

[0062]

[Table 1]

Comparative Example 1 In Example 1, when the ratio of w was 1, crystallization was not sufficient and a single crystal powder could not be obtained. The results are shown in Table 1.

Comparative Example 2 In Example 1, when the ratio of w was 0.05, the amount of crystals obtained was too small to be practical.

Example 2 0.4 mol of barium was added to 2 mol of 4 mol of methoxyethanol.
After mixing and reacting at 5 ° C, the mixture was aged at 120 ° C for 2 hours.
After that, the mixture was cooled to 90 ° C., 0.4 mol of titanium tetraisopropoxide was added and further heated to 120 ° C.,
Hydrolysis was carried out by adding 0.6 mol of water dissolved in methoxyethanol (solution A). Separately prepared barium methoxyethoxide, trimethyl borate and tetraethoxysilane were added to this solution, and Ba: B: Si = 1: a: 0.5.
A solution (B
Solution) was mixed with Solution A as shown in Table 2. Liquid composition _{0.7BaTiO 3 -0.3 (BaO-aBO 1.5} -
0.5aSiO ₂ ). This liquid was dried with a rotary evaporator to obtain a powder. 800 this powder
The powder was obtained by baking in air at 30 ° C. for 30 minutes. This powder was immersed in 1N hydrochloric acid at 50 ° C. for 10 minutes and then centrifuged to obtain a fine single crystal powder. The crystallinity of this powder was measured by the same method as in Example 1. The results are shown in Table 2.

Comparative Example 3 When a is 3.3, barium is dissolved in the glass to reduce the proportion of the crystal phase, which is not preferable.

Comparative Example 4 When a was 0.04, the crystallization was not sufficient because the glass component was too small.

[0068]

[Table 2]

Example 3 Strontium diisopropoxide, trimethyl borate, tetraethoxysilane and titanium tetraisopropoxide were mixed in a molar ratio described below and dissolved in a 1: 1 (weight ratio) isopropanol-toluene mixed solvent. Then, a solution for forming a fine single crystal powder of 15% by weight in terms of oxide was synthesized. The composition is 0.8 SrTiO ₃ -0.2 (SrO-
0.5B were ₂ O ₃ represented by the -0.1SiO _2). After this liquid is dried and made into powder, it is finally 800
It was baked in the air at 0 ° C for 1 hour. Then, it was immersed in 1N hydrochloric acid for 10 minutes, filtered and washed to obtain a fine single crystal powder having an average particle size of 5.0 μm. The crystallinity of this powder was measured by the same method as in Example 1. As a result, formation of SrTiO ₃ was confirmed.

Example 4 Lead diethoxide, zirconium isopropoxide, titanium tetraisopropoxide and tetraethoxy germanium were mixed with _0.7 PbZr _0.5 Ti _0.5 O ₃ -0.3.
(PbO-GeO ₂₎ were blended to obtain a composition of isopropanol over toluene 1: 1 (by weight) was dissolved in a mixed solvent of 15 wt% in terms of oxide solution for fine monocrystal powder form Synthesized. This liquid is dried to obtain a powder, which is then baked in the air at 700 ° C. for 30 minutes to obtain 1N hydrochloric acid,
After soaking for 1 minute, filtered and washed to obtain an average particle size of 0.8 μm
A fine single crystal powder of Formation of the PZT crystalline phase was confirmed by X-ray.

Comparative Example 5 0.5 mol of lead oxide powder having a particle size of 1 μm, 0.7 mol of titanium oxide powder having a particle size of 0.3 μm, 0.5 mol of strontium carbonate powder having a particle size of 1.1 μm, and 2 μm of particle size After 0.3 mol of silica powder was ball-milled in ethanol and dried, powder was obtained. This was molded into a pellet having a diameter of 10 mm and a thickness of 1 mm, and then fired at 800 ° C. Only a few crystalline phases were observed by X-ray, and no crystalline particles could be confirmed by a scanning electron microscope.

Example 5 500 ml of an aqueous solution prepared by mixing 0.2 mol of barium chloride, 0.2 mol of titanium tetrachloride, 0.02 mol of boric acid and 0.003 mol of acidic silica sol was adjusted to pH 8 with ammonia while stirring. To obtain a precipitate. The particle size of the primary particles of the powder obtained by filtering and drying this precipitate was 18 nm. The oxide powder obtained by firing this powder at 500 ° C. for 3 hours was ground in a mortar and then molded into pellets having a diameter of 10 mm and a thickness of 1 mm by a pressing machine. The pellets were fired in the air at 900 ° C. for 30 minutes. Then, it was immersed in 1N hydrochloric acid for 10 minutes, then filtered and washed to obtain a fine single crystal powder having a particle size of 5 to 10 μm. The crystallinity of this pellet was measured by the same method as in Example 1, and as a result, the generation of a crystal phase was confirmed by X-ray diffraction.

Comparative Example 6 0.16 mol of barium chloride and 0.04 of magnesium chloride
Aqueous solution 500 in which 0.1 mol of titanium tetrachloride and 0.2 mol of titanium tetrachloride
The ml was adjusted to pH 8 with ammonia with stirring and a precipitate was obtained. The particle size of the primary particles of the powder obtained by filtering and drying this precipitate was 18 nm. This powder at 500 ℃ 3
The oxide powder obtained by firing for a period of time was ground in a mortar and then formed into pellets having a diameter of 10 mm and a thickness of 1 mm by a press. The pellets were fired in the air at 900 ° C. for 30 minutes. This pellet was crystallized by X-ray diffraction,
No single crystal particles were observed by a scanning electron microscope.

[0074]

According to the present invention, a fine single crystal powder having a perovskite structure having a uniform composition and a uniform composition can be obtained more easily than the conventional method obtained by hydrothermal synthesis method. It can be synthesized at a low temperature and can produce fine single crystal powders of various compositions, and its industrial value is great.

[Brief description of drawings]

1 shows the particle structure of the fine single crystal powder observed at w = 0.8 in Example 1. FIG. A photo that replaces the drawing. (Magnification 50
0x scanning electron micrograph).

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[Procedure amendment]

[Submission date] May 26, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

In the case of the CVD method, the X compounds as starting materials include the following. · A lithium compounds such as Rukirurichiumu. · A sodium compound such as Le kill sodium. · A potassium compounds such as Rukirukariumu. -Organic lead compounds such as 4-ethyl lead and bis-dipivaloylmethanato lead, or lead compounds such as lead chloride such as lead chloride. -Organic barium compounds such as barium ethoxide, barium isopropoxide and bisdipivaloyl barium, or halide barium compounds such as barium chloride. -Organomagnesium compounds such as magnesium ethoxide, magnesium isopropoxide, and bisdipivaloyl magnesium, or halide magnesium compounds such as magnesium chloride. -Organic calcium compounds such as calcium ethoxide, calcium isopropoxide and bisdipivaloyl calcium, or halide calcium compounds such as calcium chloride. -Organic strontium compounds such as strontium ethoxide, strontium isopropoxide and bisdipivaloyl strontium, or halide strontium compounds such as strontium chloride. Lantern ethoxide, lanthanum acetylacetonate, an organic lanthanum compound such as tri Sujipibaroiru Metanato lanthanum, or lanthanum compound halides lanthanum chloride. Yttrium ethoxide, yttrium acetylacetonate, an organic yttrium compounds such as tri Sujipibaroiru Metanato yttrium or yttrium compound halides yttrium chloride. Bismuth ethoxide, bismuth acetyl acetate toner DOO
Or an organic bismuth compound such as bismuth chloride, or a bismuth compound of a halide such as bismuth chloride.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

In the case of the CVD method, the M compound as a starting material includes the following.・ Trimethyl aluminum, triethyl aluminum,
Aluminum compounds such as aluminum triisopropoxide, or halogenated aluminum compounds such as aluminum chloride. -Manganese compounds such as manganese acetylacetonate. -Organic titanium compounds such as titanium ethoxide, titanium isopropoxide, titanium butoxide, and titanium acetate, or halide titanium compounds such as titanium tetrachloride. Organic zirconium compounds such as zirconium ethoxide, zirconium isopropoxide, zirconium butoxide, or zirconium compounds of halides such as zirconium tetrachloride. Organic such as tetraethyltin, tetrabutyltin, tin ethoxide, tin isopropoxide, tin butoxide. Tin compounds. -Organomagnesium compounds such as magnesium ethoxide, magnesium isopropoxide, and bisdipivaloyl magnesium, or halide magnesium compounds such as magnesium chloride. -Organic zinc compounds such as zinc ethoxide, zinc acetylacetonate and bisdipivaloyl zinc, or halide zinc compounds such as zinc chloride. -Organic iron compounds such as iron ethoxide, iron acetylacetonate, and bisdipivaloyl iron, or halide iron compounds such as iron chloride. -Organic cobalt compounds such as cobalt ethoxide, cobalt acetylacetonate, and bisdipivaloyl cobalt, or halide cobalt compounds such as cobalt chloride. -Organic nickel compounds such as nickel ethoxide, nickel acetylacetonate, and bisdipivaloyl nickel, or halide nickel compounds such as nickel chloride. -Organic niobium compounds such as niobium ethoxide and niobium acetylacetonate, or halide niobium compounds such as niobium chloride. Tantalum ethoxide, tantalum acetyl acetate toner DOO
Tantalum compounds such as organic tantalum compounds such as or tantalum chlorides such as tantalum chloride. -Organic tungsten compounds such as tungsten ethoxide, tungsten acetylacetonate, and bisdipivaloyl tungsten, or halide tungsten compounds such as tungsten chloride.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

In the method using a compound soluble in an organic solvent, the M compound includes the following.・ Trimethyl aluminum, triethyl aluminum,
Aluminum compounds such as aluminum triisopropoxide, or halide aluminum compounds such as aluminum chloride. -Manganese compounds such as manganese acetylacetonate. -Titanium compounds such as tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium and titanium tetrachloride. -Zirconium compounds such as tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxyzirconium, tetrabutoxyzirconium and zirconium tetrachloride. -Tin compounds such as tetramethoxytin, tetraethoxytin, tetraisopropoxytin, tetrabutoxytin, tetraoctyltin, tin acetylacetonate and tin tetrachloride.・ Dimethoxy magnesium, diethoxy magnesium,
Magnesium compounds such as diisopropoxy magnesium and dibutoxy magnesium. -Zinc compounds such as dimethoxyzinc, diethoxyzinc, diisopropoxyzinc, dibutoxyzinc, zinc acetylacetonate and zinc chloride. Triethoxy iron, di isopropoxy iron, di-butoxy, iron acetylacetonate, iron compounds iron chloride. · Diethoxy cobalt, diisopropoxy cobalt, di <br/> butoxy, cobalt acetylacetonate, cobalt compound cobalt chloride. · Diethoxy nickel, diisopropoxy nickel, di <br/> butoxy, nickel acetylacetonate, nickel compounds such as nickel chloride. -Niobium compounds such as pentamethoxy niobium, pentaethoxy niobium, pentaisopropoxy niobium, pentabtox niobium, niobium chloride.・ Pentamethoxytantalum, pentaethoxytantalum,
Tantalum compounds such as pentaisopropoxy tantalum, pentab toxtantalum and tantalum chloride. -Tungsten compounds such as pentamethoxytungsten, pentaethoxytungsten, pentaisopropoxytungsten, pentabtoxytungsten, and tungsten chloride.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C30B 29/22 Z 8216-4G H01B 3/00 D 9059-5G H01G 4/10 4/12 415

Claims (6)

[Claims] 1. An oxide of X (X is Li, Na, K, Pb,
One or more selected from Ba, Mg, Ca, Sr, La, Y and Bi) and an oxide of M (M is Al, Mn,
Ti, Zr, Sn, Mg, Zn, Fe, Co, Ni, N
b, Ta, W, one or more kinds selected from them, an oxide of G (G is one or more kinds selected from B, As, Sb, Si, Ge, Te, P) or these X compound, M compound, and G compound that can be converted into the oxide of formula (1) are mixed so that the diameter of each oxide or compound is less than 0.1 μm, and the mixture is fired to obtain the compound of the general formula wXMO _3- (1-
During _{w) (XO y -aGO z)} ( wherein, y, z represents the number of oxygen atoms, X is Li, Na, y = 0.5 When the K, X is P
When b, Ba, Mg, Ca, Sr, y = 1, X is L
When a, Y and Bi, y = 1.5. G is B, A
When s and Sb, z = 1.5, when G is Si, Ge and Te, z = 2, and when G is P, z = 2.5. w represents the number of moles, a is a real number, and 0.1 <w ≦ 0.95,
0.05 ≦ a ≦ 2. ) Is obtained, and the glass component is dissolved and removed therefrom with an acid or an alkali, and a method for producing a fine single crystal powder. 2. An organic solvent-soluble X compound (X is Li, N
a, K, Pb, Ba, Mg, Ca, Sr, La, Y, B
1 or more selected from i), M compound (M is Al, Mn, Ti, Zr, Sn, Mg, Zn, Fe, C)
one or more selected from o, Ni, Nb, Ta and W), G compound (G is B, As, Sb, Si, Ge,
(One or more selected from Te and P) are used, and the respective solutions are mixed, dried or hydrolyzed to give a mixed powder having a diameter of each compound of less than 0.1 μm, and then calcined to obtain a powder. Formula wXMO ₃ − (1-w) (XO _y −
aGO _z ), where y and z are oxygen numbers, X is Li,
When Na and K, y = 0.5, X is Pb, Ba, Mg,
Y = 1 when Ca and Sr, and y = 1.5 when X is La, Y, and Bi. When G is B, As, Sb, z =
1.5, when G is Si, Ge, Te, z = 2, G is P
Then z = 2.5. w represents the number of moles, a is a real number, and 0.1 <w ≦ 0.95 and 0.05 ≦ a ≦ 2. ) Is obtained, and the glass component is dissolved and removed therefrom with an acid or an alkali, and a method for producing a fine single crystal powder. 3. An X compound having a primary particle size of less than 0.1 μm (X is Li, Na, K, Pb, Ba, Mg, Ca, S).
one or more selected from r, La, Y and Bi), M compound (M is Al, Mn, Ti, Zr, Sn,
One or more selected from Mg, Zn, Fe, Co, Ni, Nb, Ta, W), G compound (G is B, A
s, Sb, Si, Ge, Te, P) (one or more selected from colloidal sols) are used, and the respective colloidal sols are mixed and dried or coprecipitated so that each compound has a diameter of 0. A mixed powder of less than 1 μm is formed and then fired to obtain a powder having the general formula wXMO _3- (1-w) (XO _y -aG
O _z ), where y and z are oxygen numbers, and X is Li and N
a = K, y = 0.5, X = Pb, Ba, Mg, C
When a and Sr, y = 1, and when X is La, Y, and Bi, y = 1.5. When G is B, As, Sb, z =
1.5, when G is Si, Ge, Te, z = 2, G is P
Then z = 2.5. w represents the number of moles, a is a real number, and 0.1 <w ≦ 0.95 and 0.05 ≦ a ≦ 2. ) Is obtained, and the glass component is dissolved and removed therefrom with an acid or an alkali, and a method for producing a fine single crystal powder. 4. A water-soluble X compound (X is Li, Na,
One or more selected from K, Pb, Ba, Mg, Ca, Sr, La, Y and Bi), M compound (M is A
l, Mn, Ti, Zr, Sn, Mg, Zn, Fe, C
one or more selected from o, Ni, Nb, Ta and W), G compound (G is B, As, Sb, Si, Ge,
(One or more selected from Te and P) are used, and the respective solutions are mixed, dried or co-precipitated to obtain a mixed powder having a diameter of each compound of less than 0.1 μm, and then fired to form a powder. Formula wXMO ₃ − (1-w) (XO _y −a
GO _z ) (In the formula, y and z represent oxygen numbers, and X represents Li and N.
a = K, y = 0.5, X = Pb, Ba, Mg, C
When a and Sr, y = 1, and when X is La, Y, and Bi, y = 1.5. When G is B, As, Sb, z =
1.5, when G is Si, Ge, Te, z = 2, G is P
Then z = 2.5. w represents the number of moles, a is a real number, and 0.1 <w ≦ 0.95 and 0.05 ≦ a ≦ 2. ) Is obtained, and the glass component is dissolved and removed therefrom with an acid or an alkali, and a method for producing a fine single crystal powder. 5. A fine single crystal according to claim 1, 2, 3 or 4, characterized in that an aqueous solution of one or more selected from hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid and acetic acid is used as the acid. Powder manufacturing method. 6. The fine single crystal powder according to claim 1, 2, 3 or 4, wherein an aqueous solution of one or more selected from sodium hydroxide, potassium hydroxide and ammonia is used as the alkali. Manufacturing method.